Deaminated trisazo dye



Patented Apr. 27, 1954 UNITED STATES P'ATENT OFFICE DEAMINATED TRISAZO DYE William H. Armento, Albany, N. Y, assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 22, 1951, Serial No. 262,999

Claims. (01. 260-172 I This application is a continuation in part of application Serial Number 53,373 filed October 7, 1948. This application is now Patent No. 2,607,769 issued August 19, 1952.

This invention relates to a new class of azo dyes and particularly to trisazo dyes having a tetrazotized aromatic nucleus.

Azo dyes are derived by coupling diazo compounds with compounds designatedas coupling components. These latter, in order to perform the coupling function, must contain activating groups which promote coupling. A discussion and disclosure of such groups, which may be termed couplin promoting groups, may be found in vol. 2, page 227, of the Encyclopedia of Chemical Technology, 1948, Interscience Encyclopedia, Inc. Generally such compounds are phenols, naphthols, aromatic amines and comof a tetrazotized aromatic compound to a first coupling component containing a non-primaryamino auxochrome group, couplin the other end to a second coupling component containing a diazotizable primary amino group and capable of coupling only once, diazotizing and coupling it with a third coupling component free of coupling promoting groupsiother than diazotizable primary amino groups, and then deaminating the compound.

The new class of azo dyes are trisazo dyes free of primary amino groups and may be represented by the formula wherein R1 is a radical of a coupling component and contains a non-primary-amino auxochrome roup; D'is a radical of a tetrazotized aromatic pounds which possess enolizable lcetone groups of i an aliphatic character. In the case of the phenols, naphthols and aromatic amines the activating phenolic or amino group directs coupling "or attachment of the azqgroup to an ortho or para position depending upon theposition of the hydroxyl or amino group itself and the character "and position of other substituent group in the molecule. 7

The hydroxyl or amino activating groups in the phenols, naphthols and aromatic amines also affect the dye properties of the azo dye produced from th coupling reaction. The amino group favors the production of a bathochromic effect, that is a shift from the yellow toward blue or a deepening effect. The correspondin hydroxy or phenolic compounds are lessbathochromic in efiect. Hence, it may generally be said, that where deep colors aredesired aromatic amines should be selected as the coupling components, and phenols or naphthols where lighter colors are desired. Additional substituents such as halogen, nitro, alkyl, aryl, alkoxy and additional amino and :hydroxy groups 'having bathochromic eiiects are introduced in order to further modify the color.

compound; R is a radical of a coupling component capable of. couplingzonly once and R" is a member of the group consisting of radicals of the benzene and naphthalene series free of coupling promoting groups.

Ingeneral, any tetrazotized aromatic compound may be the nucleus of the dyestuffs of the invention. As the aforementioned first coupling component, any of the known coupling components containing non-primary-amino auxochrome group may be employed, such as phenols,

naphthols, ice-color coupling components and the like. The nature, function and identity of auxochrome groups for intensifying the color of dyestuffs is well known in the art whereby the proper selection of such operative first coupling component will be obvious to the skilled worker.

- -(Ibi-d.: page230, functions and examples of auxo- 'chromes.) Equally obvious will be the selection of the proper intermediates for use as the afore mentioned second and third coupling components, which are essentially phenyl and naphthyl con- "taining compounds. It will be understood that the tetrazotized nucleus and coupling components may contain substituent groups which do not "j Thegroups added for bathochromic purposes,

'shade modifying groups, groups, and the-like.

interfere with the progress of the reaction for producing the desired results, as for example water solubilizing These deaminated dyes have excellent substantivity for leather, dyeing level and penetrating more deeply than the correspondin undeaminated'dyes. They haveexcellent alkali solubilities. Some of these dyes are alsovexcellent textile dyes, particularly on union material -such as cotton-wool, cotton-rayon, wool-rayon, jmercerized cotton and rayon tubing. They have good COOH chloric acid are added and the combination rediazotized with 77 parts sodium nitrite at 20 C. for 2 hours. 150 parts sodium formats are added and the mixture is heated to 70 C. for one hour. The product is salted with NaCl solution and isolated by filtration. When dried, a dark violet-brown powder is. obtained which is soluble in alkali to a clear brown solution. The formula of the product is:

replaced by hydrogen. In the case of the acetate reduction there may be side reactions resulting in some methylationjormation or biaryls and other products, but the formate results almost exclusively in the hydrogen replacement. Hence, although the acetate reduction works well in some instances, the formate process is generally preferred.

OOOH

It corresponds to Dye No. in the table below.

EXAMPLE 2 xample l is repeated, except that Laminonaphthalene-Tsulionic acid is substituted for 1-an1inonaphthalene-S-sulfonic acid in both instances. The formula of the product is:

In carrying out the reduction process with formate or acetate an aqueous solution of the diazonium salt or the diazotization solution maybe employed. Sufficient formate or acetate is added to neutralize all the free mineral acid in the solution and the acid formed during deamination. The reaction will take place at low temperature, but optimum results are obtained by raising the temperature to 60 to 70 C. and maintaining it at that level for one hour. Higher temperatures and shorter reaction times may be employed if desired.

- The following examples. will serve to further illustrate the invention, it being understood that the conditions, materials and quantities are not intended to be critical or to place any limitation on the scope of the invention. Parts are by weight unless otherwise indicated.

EXAMPLE 1 184 parts of benzidine are tetrazotized in the usual manner. To the neutralized tetrazo are added 145 parts of salicylic acid inslightly alkaline solution. 220 parts soda ash were then added and the mixture stirred at 5 to 10 C. until the monazo coupling. is; complete. A solution of 230 parts l-aminonaphthalene-G- sulfonic acid is then added: and the combination stirred overnight. The combination is diazotized with 629 parts hydrochloric acid and 75 parts sodium nitrite at 1520 C. for two hours. The diazo is run into a solutionof 240 parts l-aminonaphthalene-G-sulfonic acid containing 400 parts sodium acetate crystals and stirred over night at 10? to 15C. In the morning, 525 parts hydro- OgH 50311 It corresponds to Dye No. 23 in the table below.

EXAMPLE 3 Example 1 is repeated, except that instead of using l-a1ninonaphthalene-6sulionic acid, a mixed Cieves acid is employed. This is a mixed l-arnino-naphthalene-S(and 7) -sulfonic acid. The formula of the product is:

The product is a violet brown powder having good solubility, and dyes vegetable fibers and leather a full rich brown shade.

EXAMPLE 2 184 parts 01 benzidine are tetrazotized in the usual manner. To the neutralized tetrazo are added parts of salicylic acid in a slightly alkaline solution. 220 parts of soda ash are then added and the mixture stirred at 38 C. until the monoazo coupling is complete. The solution is made slightly acid and 137 parts slightly acidified 5unethyl-o-anisidine is added and stirred well for about hour. 150 parts sodium acetate are added as a 20% solution. Soda ash is then added to render the solution slightly alkaline. After overnight stirring the changev is acidified and filtered.

The filtered product is sludged in acid solution and diazotized with 69 parts sodium nitrite solution at 19--23 C. The diazo is run into a slightly acidified solution of 223 parts l-aminonaphthalene-G-sulfonic acid containing 300 parts sodium acetate crystals and stirred at about 10 C. overnight.

The charge is acidified, the temperature adjusted to about 19-23 C. and 69. parts sodium nitrite solution added and maintained torabout 2 hours. 150 parts sodium formate are added COOH and the mixture heated to 80-85 C. for about A hour.

The product is salted with NaCl solution, filtered and dried. The formula of the product is:

COOH

OCH:

It corresponds to Dye No. of the table below.

EXAMPLE 5 Example 4 is repeated, except that the 5- methyl-o-anisidine isreplaced by 153 parts 2- amino-1,4-dimethoxybenzene. The formula of the product is:

coon methoxybenzene is employed. The formula of the product is OCH:

It corresponds to Dye No. 25 of the table below.

EXAMPLE 7 Example 4 is repeated, except that after the ion last diazotization, there is substituted for 150 parts sodium formate. 300 parts sodium acetate.

The properties of the product are practically identical to those obtained in Example 4 except that the shades are slightly duller.

In the following tables there are listed a num- OCH! OCH:

It corresponds to Dye No. 18 of the table below. I

EXAMPLE 6 Example 1 is repeated, except that in the case of the final 'coupling, .153 parts 2-amino-L4-dihave the indicated properties.

her of combinations of components which upon being reacted and deaminated in a manner similar to the procedure of the foregoing examples,

-- Table No. R D R R" Cotton Dyeings on wool Leather 1 Salicylic acid Dianisidine l-Aminonaphthal-Aminonaphtha- Weak red Weak yellow Brown.

lene-fi-sulionic lene-B-sulfonlc brown. brown. Y 7 acid. v acid. Phenylm'ethylpyrdo .do -.do Dull Weak Vio- Weak red Red brown.

azolone. t. brown. Resorcinol .do do ..do Weak dull red Very weak red Do.

- violet. brown. l-Naphthol do ..do..... do Weak dull red Weak red Yellow brown.

, gray. brown. 2-Naphthol-6-su1- Weak dull Very weak Violet.

ionic acid. blue. pink. Phenol Dgll dark Dark brown" Dark brown.

rown. Acetoacetanilide Dgll yellow Yellow brown. Yellow brown.

rown. 8 Z-Naph t h 01-3, 6- Weak dull vio- Very weak red Violet. disulfonic acid. let. brown. 9 2-hydroxy-3-naph- .do Weak dull Red gray.

thoic acid. gray. 10 1-Naphthol-3-,8- Dull red vio- Very weakred Red brown.

disulfonic acid. brown. 11 2-Hydroxy-3- Weak dull vio- Dull violet.-. Violet.

naphthanilide. 4 let. 12 Salicylic acid Benzidine m-Toluidine Dull brown". Dullbrown.-- Brown. d d o-Anisidine- Yellow brown. Yellow brow-m Do.

2-Amino-5naph- Dull blne Weak dull red Red blue.

thggJ-sulfom'c blue. aci fi-Methyl-o-anisll-Amindnaphtha- Strong bright Strong bright Brown.

dme. leng-G-sulfonic brown. brouui. aci 16 do do o-To1uidine do Strong brown. Brgght red Yellow brown,

. I I rown. 17 do .do l-Amino-naphthado- Strong red do D lene. brown. 18 do .do 2-Amin0-l, 4-dldo "do ..do Red brown.

methoxy-ben- V I zene. 19 z-Hydroxy-s-naphclo l-Aminonaphthado. Dull-violet... Dull vlolet Violet.

thoic acid. leng-o-sulfonic. I

am r Acetoacetanilide do .do .do Very weak dull Very weakdull Very light brown. brown. brown.

2-Hydroxy-3-naphdo .do ......d0 Weak dull Dull blue-.... Violet,

thanillde. blue.

Table-Continued No. R D R R Cotton Dyeings on wool Leather 22 Salicylic acid Benzldlne l-Aminonaphthal-Arninonaphtha- Brown Brown Brown.

lene-fi-sulionic lene-7-sulfonic acid. acid. 23 do do l-Aminonaphthado Yellow brown Yellow brown- Yellow brown.

lene-7-sulionic ac1 24 do do l. l-Amino-naphtham-T01uidine Dullred brown. Red brown". Brown.

Iene-G-sulfonic acid. 25 do do do 2-An1ino-l,4-di- Dark brown do Dark brown.

methoxybenzene. 26 do do .-do m-Phenylene-di- Strong brown. Weak dull Do. amine. brown. 27 do B e n zi din e 2,2 l-Amino-naphtha- Weak brown Weak brown Weak brown.

disulfonic acid. lene-fi-sulionic stain. stain.

28 .do 'loluidine. Dull brown. Dullred brown. Yellow brown.

3,3Dichlorobe Dull yellow Yellow brown. D0. 2' inc. brown. 4,4-1 i3min0benz- Yellow brown .do Do.

an e. 4,4-Diamino-2,2- do Very weak Does not dye Dull brown.

stilbene-disulbrown. ionic acid. 4,4-Di-aminodo Very weak Orange brown. Orange brown. azoxy-benzene. red brown. 33 do 3,3-Diamino-diindo Very weak Weak brown" Brown.

phenylurea. brown. 34 do Benzidine l-AmiIio-naplithal-Amino-naphtha- Brown Brown Do.

lene-5-sullonic lene-fi-sultonic acid. acid. 35 do do l-Amino-naphthal-Amino-naphthado do D0.

lene-6-sulfonic lene-fi-sulionic acid. acid.

Various modifications and variations of this 30 invention will be obvious to a worker skilled in the art and it is understood that such modifications and variations are to be included within the purview of this application and'the spirit and scope of the appended claims.

I claim:

,1. Trisazo dyes free of prima ry amino groups COOH and characterized by the structural formula:

RN==NDN=NR'N=N- COOH wherein R, is a radical of a coupling component COOH and. contains a non-primary-amino auxochrome COOH group; D is a radical derived from a tetrazotized aromatic compound which contains two phenylene nuclei; R is a radical'derived froma' coupling component capable of couplin only once and R" is a member of the group consisting of radicals of 35 the benzene and naphthalene series free of coupling promoting groups.

2. The dyestuff of the formula:

The dyestufi' of the formula:

4. The dyestuff of the formula:

5. The dyestuff of the formula:

OxH

7. A process comprising coupling one end of a tetrazotized aromatic compound which contains two phenylene nuclei to a first coupling com ponent containing a non-primary-amino auxochrome group, coupling the other end to a second coupling component containing a diazotizable primary-amino group and capable of coupling only once, diazotizing and coupling it with a third coupling component free of coupling promoting groups other than diazotizable primaryamino groups, and then deaminating the compound.

8. A process comprising coupling one end of a tetrazotized aromatic compound which contains two phenylene nuclei to a first coupling component containing a non-primary-amino auxochrome group, coupling the other end to a second coupling component containing a diazotizable primary-amino group and capable of coupling only once, diazotizing and coupling it with a third coupling component free of coupling promoting groups other than diazotizable primary-amino groups, and then deaminating the compound by diazotizing and reacting it with a member of a group consisting of alkali metal formate and alkali metal acetate.

9. A process comprising coupling one end of a tetrazotized aromatic compound which contains two phenylene nuclei to a first coupling component containing a non-primary-amino auxochrome group, coupling the other end to a second 10 coupling component containing a diazotizable OCH:

OCH:

primary-amino group and capable of coupling only once, diazotizing and coupling it with a third coupling component free of coupling promoting groups other than diazotizable primary-amino groups, and then deaminating the compound by diazotizing and reacting it with sodium formate.

10. A process comprising coupling one end of a. tetrazotized aromatic compound which contains two phenylene nuclei to a first coupling component containing a non-primary-amino auxochrome group, coupling the other end to a second coupling component containing a diazotizable primary-amino group and capable of coupling only once, diazctizing and coupling it with a third coupling component free of coupling promoting groups other than diazotizable primary-amino groups, and then deaminating the compound by diazotizing and reacting it with sodium acetate.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 399,581 Strasburger Mar. 12, 1889 515,381 Ulrich et a1. Feb. 27, 1894 515,897 Bracl: Mar. 6, 1894 516,381 Rudolph Mar. 13, 1894 693,6e6 Krekeler et al. May 10, 1898 2,155,001 Schmid Apr. 18, 1939 2,174,998 Rossander Oct. 3, 1939 

2. THE DYESTUFF OF THE FORMULA: 